Localized Treatment for DBP s using Spray Aeration and Online Monitoring Tom Williams +1 408 476 7768 twilliams@aquametrologysystems.com Tom.Williams@enebio.com
Who are we? Worked in DBP s since 2008 AMS is US based company with R&D and Technical Support in Sunnyvale, CA and manufacturing in Lowell, MA Privately held with European and US private investors Founded in 2007 to focus on TTHM Monitoring now also HAA and Trace Metals Monitoring Established presence across the USA and in UK and Spain with multiple units at several clients THM-100 has been extensively tested independently by leading laboratories and water utilities in USA and Europe Enabling the Optimization of THM Control 2
Disinfection By-Product Formation DBPs Naturally-Occurring Organic Matter (NOM) e.g. - Humic Acids - Fulvic Acids Chlorine Based Compounds for Microbiological Disinfection e.g. - Chlorine - Hypochlorite - Chlorine Dioxide Disinfection By-Products* e.g. - Trihalomethanes - Haloacetic Acids -Bromate - Chlorite Disinfection By-Products* - Several thousand are known - More than 500 have been toxicologically reviewed - Several classes and compounds are regulated in drinking water: Trihalomethanes Haloacetic Acids 3
Typical Surface Water Source Enabling the Optimization of THM Control 4
DOC or TOC Detection Enabling the Optimization of THM Control 5
Hydrophilic or Hydrophobic? Enabling the Optimization of THM Control 6
Typical Humic compound the methanes Enabling the Optimization of THM Control 7
Halogens the Halo s in THM s halogen molecule structure model d(x X) / pm (gas phase) d(x X) / pm (solid phase) fluorine F 2 143 149 chlorine Cl 2 199 198 bromine Br 2 228 227 iodine I 2 266 272 Enabling the Optimization of THM Control 8
Bromine sources Mining areas salt/coal Fire retardants Drugs and Pharmaceuticals DBDMH Cooling towers/pulp and paper mills Dyes Organobromine Biocides water treatment Salt Water Intrusion Enabling the Optimization of THM Control 9
Trihalomethanes in Drinking Water chloroform bromodichloromethane dibromochloromethane bromoform 10
Stage 1 Disinfection By Product Rule Source: EPA, 40 CFR Parts 9, 141, and 142 National Primary Drinking Water Regulations Stage 2 Disinfectants and Disinfection Byproducts Rule; Final Rule, p 411 11
Stage 2 Disinfection By Product Rule Source: EPA, 40 CFR Parts 9, 141, and 142 National Primary Drinking Water Regulations: Stage 2 Disinfectants and Disinfection Byproducts Rule; Final Rule, p 411 12
Standard Method for DBP Analysis Operator collects a water sample Physically delivers it to the lab A skilled technician prepares the sample The sample is analyzed on an expensive piece of lab equipment (GC-MS) Results are reported to the water treatment plant in 3-10 days Operator makes an educated adjustment to the treatment process Water utility puts the report in a binder 13
Operating a Plant Without a Monitor Is Like Driving a Car Without a Speedometer Enabling the Optimization of THM Control 14
AMS THM-100 Another Option First commercial in-line instrument for TTHM and CHCl 3 monitoring with manual sampling capability Installed at multiple water utilities with excellent correlation to lab results Unattended 24/7 results in 1 hour which can immediately be used to modify the process Self calibrating no need for skilled operator intervention at anytime 5-200 (in μg/l) range for TTHM and Chloroform 2 (W) x1.3 (D) x 5 (H) 100 lbs 15
Organization of THM-100 System W 2.0 (610mm), D - 1.33 (406mm) H 5.0 (1,524mm) Weight 100lbs (45.3kg) Electronics Cabinet Process Cabinet Chemical Reagents and Standards www.ams-h2o.com 16
THM-100 Principal of Operation Analysis Steps THM-100 Process Flow Draw Finished Water Sample Fill Reservoir (Purge Vessel) Extract THMs Purge Reservoir and Trap THMs Concentrate THMs Desorb Trap and Dissolve THMs into Reagents React THMs with Reagents Initiate the Fujiwara Reaction Measure change in Absorbance Spectrophotometric Detection at 540 nm Determine Concentration of the dominant THM and TTHM Quantitative Determination of dominant THM and TTHM Concentrations Report total THM and Chloroform results Make Results Available on the System and via 4-20 ma and the Ethernet 17
Rates of the Colorimetric Reactions Rates of Colorimetric Reactions Chloroform reacts more slowly than brominated THMs to form the Fujiwara reaction The THM Speciation of each water sample is deduced from the kinetics of the Fujiwara reaction Optimized Fujiwara Reaction Kinetics for the Four THMs 0.45 0.40 0.35 Absorbance.e 0.30 0.25 0.20 0.15 0.10 0.05 0.00 Cl3 Br2Cl BrCl2 Br3 0 100 200 300 400 500 600 700 800 900 1000 Time / secs www.ams-h2o.com 18
Data Reliability: Labs vs. Online (Spiked Samples) 5 US-EPA Accredited Labs & 3 THM-100 Monitors (current studying 60 labs nation wide) Sample Water Spiked at TTHM 79.5 ug/l (60% CHCl 3 ) Lab 1 Lab 2 Lab 3 Lab 4 Lab 5 THM 100 1 THM 100 2 THM 100 3 30 30 % Error CHBr1-3 20 10 0 10 20 % Error CHBr1-3 20 10 0 10 20 30 30 20 10 0 10 20 30 30 30 20 10 0 10 20 30 % Error CHCl3 % Error CHCl3 19
70 THM Measuremnts Online vs Three Analytical Labs CHCl3 Conc Lab [ALS] 60 TTHM Conc Lab [ALS] TTHM Lab [Microbac Harrisburg] TTHM Lab [Benchmark] 50 CHCl3 Conc Online TTHM Conc Online TTHM and % CHCl3 40 30 20 10 0 11/14 11/28 12/12 12/26 1/9 1/23 2/6 2/20 20
What Influences THM Formation? Time (increase in water age = increase in THMs) Temperature (increase in temperature = increase in THMs) ph Disinfectant dose Natural organic matter (NOM) Seasonal effects high temperature, changes in water quality 21
Managing TBP Formation at the WTP Remove precursors at the water treatment plant Enhanced coagulation Optimizing coagulant type (alum, ferric chloride, PACl) and dosage based on source water quality GAC adsorption Engineered Bio filtration Membranes RO filtration Delay introduction of disinfectant Use alternate disinfectants Chlorine dioxide Chloramines Ozone 22
Distribution System DBP Management Techniques Reduce water age / chlorine demand Promote system turnover Operational changes Mixing systems Dead end elimination Water quality based flushing program 23
What is Happening in the Tank? Instability due to short circuiting (no fresh chlorine in upper layers) Chlorine residuals decay rapidly Buoyant warmer water floats persistently DBPs / Nitrification Biofilm grows in warmer layers Instability due to lack of turnover (no fresh chlorine 24 in upper layers)
Tank Mixing Results East Tank June July 2010 25
Localized Removal of THMs in the Distribution System External aeration systems Packed tower or forced draft Tray aerator In tank / reservoir aeration systems Surface aeration Spray aeration Diffused bubble aeration 26 GAC contactors Chlorine booster station required
Typical In Tank / Reservoir Aeration Systems Recirculation and Surface Spray System Diffused Bubble Aeration System Surface Mechanical Aerator System THM removal via liquid / gas transfer
Case Study - Full Scale Demonstration Ongoing Projects Spray Tank Aeration 28
Case Study- Full-Scale Aeration System 29
Case Study - Full-Scale Aeration System 140 120 382 376 100 370 80 60 40 364 358 352 20 346 0 30 340 6/15/14 12:00 AM 6/20/14 12:00 AM 6/25/14 12:00 AM 6/30/14 12:00 AM 7/5/14 12:00 AM 7/10/14 12:00 AM 7/15/14 12:00 AM 7/20/14 12:00 AM TTHM (ug/l) Tank Level (ft) Mashantucket Pequot Tribal Nation Water Treatment Simulation Study Results Aeration System Aeration System On TTHM Level During Tank Fill TTHM Level During Tank Drain Tank Level
Independence Tank - NKWD 1 million gallon capacity Source = FTTP/TMTP Blend Demand 2 MGD Influences 2 THM compliance sites 3 drain/fill cycles daily 450,000 gallon per day turnover ~20% flows through tank Booster chlorine up and downstream
Case Study low mixing energy (velocity contour plot) > 0.1 ft/s 0.1 mgd spray spray pattern (blue) 1.1 mgd fill
Case Study Low mixing energy (tracer concentration plot) 100% new water 50/50 blend t = 5 min t =30 min 100% old water t =60 min t =120 min
NKWD Lab Results vs. On Line Analyzer 80 70 60 TTHM Concentration (ug/l) 50 40 30 Lab Total AMS Total 20 10 0 6/25/2013 8/14/2013 10/3/2013 11/22/2013 1/11/2014 3/2/2014 4/21/2014 6/10/2014 Date
City of Phoenix South Mountain Reservoir Enabling the Optimization of THM Control 35
Optimizing Energy Use for THM Remediation System installed May 2012 Location is the last point in the network where remediation can occur TTHM levels too close to MCL without remediation 10-30 ug/l daily swing aeration, pumping, temperature, demand 8 15-HP aerators which can only be turned on or off 8 15-HP aerators, using 784MWH/year ug/l 90 100 80 90 70 80 60 70 60 50 50 40 40 30 30 20 20 10 10 0 0 9/2/12 9/4/12 9/6/12 9/8/12 9/10/12 9/12/12 9/14/12 9/16/12 9/18/12 9/20/12 % TTHM TTHM %CHCl3 Enabling the Optimization of THM Control 36
Castelldefels Water Storage Spain B A A B Near Barcelona 330k gals/tank A - aerated B - control Enabling the Optimization of THM Control 37
THM Mitigation by Aeration, RO, & Monitoring TTHM (ug/l) Reservoir filling between midnight and 6am (lower energy costs) Aeration reduces TTHM by ~30% daily Aeration changes THM speciation Extent of aeration and RO reduced on Sept 14 th 45 40 35 30 25 20 15 10 Reduction in Extent 40 of THM Mitigation 30 5 10 0 8 Sep TTHM % Bromoform 9 Sep 10 Sep 11 Sep 12 Sep 13 Sep 14 Sep 15 Sep 16 Sep 17 Sep 18 Sep 19 Sep 20 Sep 90 80 70 60 50 20 0 % Bromoform 38
Contract Compliance Monitoring - Agbar THM / ug/l 110 100 90 80 70 60 50 40 30 20 10 THMs at Service Reservoir in NE Spain (#1) CHBr3 CHBrCl2 + CHBr2Cl CHCl3 0 14 Mar 21 Mar 28 Mar 4 Apr 11 Apr 18 Apr 25 Apr 2 May 9 May 16 May Source: Miquel Paraira Faus, Director Water Quality
City of Benicia Water Treatment No. CA 12 MGD Seasonally variant local sources Blending and enhanced coagulation Enabling the Optimization of THM Control 40
THM SUMMARY Quarterly Average Running Annual Average 120 100 80 60 40 20 0 THM conc. ug/l Jan-08 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 Oct-08 Nov-08 Dec-08 Jan-09 Feb-09 Mar-09 Apr-09 May-09 Jun-09 Jul-09 Aug-09 Sep-09 Oct-09 Nov-09 Dec-09 Jan-10 Feb-10 Mar-10 Apr-10 May-10 Jun-10 Jul-10 Aug-10 Sep-10 Oct-10 Nov-10 Dec-10 Jan-11 Feb-11 Mar-11 Apr-11 May-11 Jun-11 Jul-11 Aug-11 Sep-11 Oct-11 Nov-11 Dec-11 Jan-12 Feb-12 Mar-12 Apr-12 May-12 Jun-12 Jul-12 Aug-12 Sep-12 Oct-12
DAILY THM-100 DATA Daily Average TTHM, ppb 70.0 60.0 50.0 Total THM, ppb 40.0 30.0 20.0 10.0 0.0 10/01/12 10/15/12 10/29/12 11/12/12 11/26/12 12/10/12 12/24/12 01/07/13 01/21/13 02/04/13 02/18/13
SOURCE WATER CHANGES Blend PSC NBA Avg Daily THM 70 60 50 Total THM, ppb 40 30 20 10 0
Old Bridge Municipal Water Authority - NJ Enabling the Optimization of THM Control 10M gal tank fed from a consecutive source Few homes / low demand Variable THMs 44
Source Blend Variability in a Consecutive System System Features, Functions, Benefits Enabling the Optimization of THM Control 45
Why monitor THM s in real time? THM100 enables Real-Time Monitoring of THMs in Drinking Water THM s can vary dramatically over a few hours WHO: Engineers designing capital or operational changes need to accurately map the fluctuations in the system to provide best solution Wholesalers and Purchase Water Systems - Contract compliance between consecutive systems. Operators can test automatically at any location and also bring grab samples from around the network. WHY: Capital and operational savings can be in the $millions Operational Benefits: Reduced operating costs with process optimization of THM remediation Performance can be improved with correct blending Save Energy on aeration To identify when Bromo based THM s occur in systems Regulatory Benefits: Enables Compliance Management Archival to Proactive Minimizes Public Health Hazards from exposure to contaminants Minimizes Potential Regulatory Breaches, and Fines based on Violations 46
Other Products available HAA monitor currently being tested by Scottish Water Trace Detect Online trace metals monitors arsenic, selenium, iron, manganese, chromium, many more metals Enabling the Optimization of THM Control 47
Questions Rex Sistek Aqua Metrology Systems rsistek@aquametrologysystems.com (602) 370 1001 Tom Williams twilliams@aquametrologysystems.com www.aquametrologysystems.com Enabling the Optimization of THM Control 48